Organosilicon compounds containing phosphorus and nitrogen



United States Patent M 3,203,924 ORGANGSILICGN COMPOUNDS CONTAINING PHOSPHORUS AND NITRGGEN Frank Fekete, Monroeville, Pa., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Filed July 25, 1960, Ser. No. 44,882 23 Claims. (Cl. 260-465) This invention relates to novel organosilicon compounds which contain phosphorus and nitrogen.

The compounds of this invention include hydrocarbonoxysilanes and siloxanes containing a trivalent phosphorus atom which is bonded to from 0 to 2 monovalent hydrocarbon groups, halogen-substituted monovalent hydrocarbon groups or hyrocarbonoxy groups and which is also bonded to from 1 to 3 nitrogen atoms, each of which nitrogen atoms is also bonded to a hydrocarbonoxysilyl or siloxysilyl group through at least three carbon atoms of a divalent hydrocarbon group. Also included among the compounds of this invention are polymers produced by hydrolyzing and condensing those hydrocarbonoxysilanes and siloxanes of this invention wherein the phosphorus atom is bonded to at least one hydrocarbonoxy group.

The hydrocarbonoxysilanes of this invention are represented by the formula:

wherein Z is a monovalent hydrocarbon group, a halogensubstituted monovalent hydrocarbon group or a hydrocarbonoxy group, R is a monovalent hydrocarbon group, R is a hydrogen atom or a monovalent hydrocarbon group, R" is a divalent hydrocarbon group, m has a value from 0 to 2 inclusive (preferably 2), n has a value from O to 2 inclusive and each nitrogen atom is interconnected to a silicon atom through at least three carbon atoms.

Illustrative of the monovalent hydrocarbon groups represented by Z, R and R in Formula 1 are the linear alkyl groups (for example the methyl, ethyl, propyl, butyl and stearyl groups), the cyclic alkyl groups (for example the cyclohexyl and cyclopentyl groups), the linear alkenyl groups (for example the vinyl and the allyl groups), the cyclic alkenyl groups (for example the cyclopentenyl and the cyclohexenyl groups), the aryl groups (for example the phenyl and naphthyl groups), the alkaryl groups (for example the tolyl group) and the aralkyl groups (for example the benzyl and beta-phenylethyl groups).

Illustrative of the divalent hydrocarbon groups represented by R in Formula 1 are the linear alkylene groups (for example the trimethylene, (CH and the octadecamethylene, (CH groups, the arylene groups (for example the naphthylene, -C H and paraphenylene, --C H groups); the cyclic alkylene groups (for example the cyclohexylene C H group); the alkarylene groups (for example the tolylene, CH C H group) and the aralkylene group (for example the -CH C H CHCH CH group) Illustrative of the halogen-substituted monovalent hydrocarbon groups represented by Z in Formula 1 are the linear haloalkyl groups (for example the chloromethyl, gamma-chloropropyl, delta-bromobutyl, omegabromostearyl and the like), the cyclic haloalkyl groups (for example the chlorocyclohexyl and chlorocyclopentyl groups), the linear haloalkenyl groups (for example the chlorovinyl and the bromoallyl groups), the cyclic alkenyl groups (for example the bromocyclopentenyl and the bromocyclohexenyl groups), the haloaryl groups (for example the chlorophenyl and bromonaphthyl groups), the haloalkaryl groups (for example the chlorotolyl group) and the haloaralkyl groups (for example the chlorobenyl and the bromophenylethyl groups).

ZmP

3,203,924 Patented Aug. 31, 1965 Illustrative of the hydrocarbonoxy groups represented by Z in Formula 1 are the alkoxy groups (for example the methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy and n-pentoxy groups) and the aryloxy groups (for example the phenoxy group).

The preferred silanes of this invention are those represented by Formula 1 wherein Z, R and R each individually contain from 1 to 18 carbon atoms and wherein R" contains at least 3 carbon atoms, and most preferably from 3 to 5 carbon atoms, interconnecting silicon and nitrogen but contains not more than 18 carbon atoms.

Illustrative of the silanes of the invention are:

CICQHEP H i: 2)a- 2 03]: The siloxanes of this invention contain a group represented by the formula:

r r ZmP[N R SlO wherein Z, R, R, R", m and n have the above defined meanings and each nitrogen atom is interconnected to silicon through at least three carbon atoms.

Illustrative of the siloxane groups represented by Formula 2 are the groups having the formulae;

' C 11 N(CH2)aSiOr.5 2

5 CICsHrP N(CH2)4SiOL5 2 and CH3 P N(CHz)aSiO1.5 a

The siloxanes of this invention include those siloxanes that are composed solely of groups represented by Formula 2 and also include those siloxanes that contain one or more groups represented by Formula 2 together with one or more groups represented by the formula:

wherein R has the above-defined meaning and x has a value from to 3 inclusive.

Illustrative of the groups represented by Formula 3 are: the SiO phenylsiloxy, methylsiloxy, dimethy-lsiloxy, methylethylsiloxy, trimethylsiloxy, diphenylsiloxy, vinyl (methyl)siloxy, divinylsiloxy, methyldiphenylsiloxy, and dicyc-lohexylsiloxy groups and the like.

The hydrocarbonoxy silanes and siloxanes of this invention are advantageously prepared by reacting a silicon compound (i.e., a hydrocarbonoxysilane or a siloxane) having an amino group interconnected to silicon through a divalent hydrocarbon group with a phosphorus compound composed of a trivalent phosphorus atom bonded to from 1 to 3 halogen atoms, each of the remaining valences of the phosphorus atom being filled by a monovalent hydrocarbon group, halogen-substituted monovalent hydrocarbon group or a hydrocarbonoxy group.

The reaction is represented by the skeletal equation:

wherein Z, R, R and m have the above-defined meanings, X is a halogen atom (preferably chlorine or bromine) and the 'free valences of the silicon atoms bond the silicon atoms (in the case of silanes) to at least one hydrocarbonoxy group or (in the case of siloxanes) to at least one siloxy group and any remaining free valences of the silicon atoms bond the silicon atoms to a monovalent hydrocarbon group.

The process is best carried out by forming a reaction mixture of the silicon compound used as a starting material and the phosphorus compound used as a starting material and maintaining the reaction mixture at a tem perature at which the desired reaction occurs while continuously removing from the reaction zone hydrogen halide [HX in Equation 4] as it is formed in the reaction.

The mole ratio of the phosphorus compound and the silicon compound employed in the reaction represented by Equation 4 are not narrowly critical. Stoichiometric amounts, i.e., the relative molar amounts indicated by the above equation, are preferred for efficient reaction and ease of product recovery. For example, one gram atom of the nitrogen-bonded hydrogen of the silicon compound desired to be displaced is preferred for each gram atom of phosphorus-bonded halogen of the phosphorus compound. The use of no more than stoichiometric amounts of the starting phosphorus compound is especially desirable when R in Equation 4 is a hydrogen atom in order to minimize the production of products having two phosphorus atoms bonded to a nitrogen atom.

The temperature at which the reaction represented by Equation 4 is conducted is not narrowly critical and can be varied in accordance with the speed of reaction desired. Temperatures of C. to 300 C. are advantageous in providing a smooth reaction and high yields of products. Temperatures below 20 C. can be employed if desired but the reaction rate is slowed. Temperatures above 300 C. can also be employed but the likelihood of reduced yields is greater and the expense of operating at such high temperatures is undesirable. The process is advantageously carried out at atmospheric pressure or at whatever pressures exist in the particular the hydrogen halide formed in the process.

reaction vessel employed without purposely applying increased or reduced pressures (i.e., autogenous pressure). Sub-atmospheric or super-atmospheric pressures can be employed, however, if desired.

No catalysts are required to effect the reaction represented by Equation 4 although suitable catalyst such as tetramethyl ammonium chloride, trimethyl benzyl ammonium chloride and the like can be employed for whatever advantage they may provide. Solvents also are not required but under certain conditions are useful in simplifying the handling of the reaction mixture or reducing the reaction time by providing a homogeneous reaction mixture if such is not otherwise obtainable. If a solvent is employed xylene, toluene, benzene, methylethyl ketone, dimethyl formamide, and the like can be used. A solvent whichdissolves the starting materials and the products but does not dissolve hydrogen halides is particularly useful in removing the hydrogen halides from the reaction zone. Such solvents include toluene, benzene, Xylene, dimethyl formamide, and the like.

The hydrogen halide (HX) formed in the reaction represented by Equation 4 is preferably continuously removed from the reaction zone by any suitable method of which many are known. A particularly suitable method is to add to the reaction mixture a hydrogen halide acceptor in the approximate stoichiometric amounts based on the amount of hydrogen halide expected to be formed in the reaction. Tertiary amines (e.g., trimethyl amine, pyridine, tn'butyl amine, and the like) are some of the excellent hydrogen halide acceptors. Such tertiary amines form salts with the hydrogen halide which salts are insoluble in the reaction mixture. Excess amounts of the acceptors over and above the stoichiometric amounts is preferably employed to ensure the substantially complete removal of the hydrogen halide. Alternately, the hydrogen halide can be continuously removed by heating the reaction mixture to cause the hydrogen halide to be evolved from the reaction mixture. Although it is not necessary in order to obtain a product, it is preferable, no matter what particular technique is employed in removing hydrogen halide, to maintain the pH of the system above a pH of about 6 and below a pH of about 8. It is preferable to maintain the pH above about 6 to prevent decreased yields due to possible side reactions involving It is preferable to maintain the pH below about 8 to prevent possible side reactions involving the silicon compound (e.g., reactions between the silicon compound and strongly basic hydrogen halide acceptors in the event moisture is also present).

The compounds of this invention can be isolated at the completion of the reaction represented by Equation 4 by any suitable conventional means. Thus the relatively low boiling compounds of this invention (i.e., in general, the hydrocarbonoxysilanes) can be isolated by filtration to remove insoluble salts and then fractional distillation of the filtrate. The relatively high boiling compounds of this invention (i.e., in general, the siloxanes) can be isolated by stripping foreign material, extraction, filtering and/or recrystallization. One or more of the various conventional means can be employed to isolate the compounds of this invention.

The phosphorus compounds employed as starting materials in the above-described process for producing the compounds of this invention are represented by the formula:

wherein Z, X and m have the above-defined meaning. The preferred starting phosphorus compounds are those as described above wherein the phosphorus-bonded monovalent hydrocarbon groups, halogen-substituted monovalent hydrocarbon groups and/ or hydrocarbonoxy groups each contains from 1 to 18 carbon atoms, In is two and x S is chlorine or bromine. Illustrative of specific phosphorus compound starting materials are and PCl The silicon compounds employed as starting materials in the above-described process for producing the compounds of this invention include both hydrocarbonoxysilanes and siloxanes that contain an amino group interconnected to silicon through a divalent hydrocarbon group. The hydrocarbonoxysilanes used as starting materials in producing the hydrocarbonoxysilanes of this invention are represented by the formula:

HI TRS i(O R) 3-11 wherein R, R, R and n have the above-defined meanings the nitrogen atom is interconnected to silicon through at least three carbon atoms. Illustrative of these silanes are gamma-aminopropyltriethoxysilane, para-aminophenyltrimethoxysilane, delta-aminobutyl(diphenyl)ethoxysilane, epsilon-amino-pentyl(methyl)dipropoxysilane, N-methyldelta aminobutyltriethoxysilane, aminomethylphenyldi phenylmethoxysilane,

N-propyl-para aminophenyl(ethyl)dimethoxysilane, N- ethyl-gamma-aminopropyltriethoxysilane, delta aminobutyltripropoxysilane, para aminophenyl(methyl)diethoxysilane and the like.

The siloxanes that are used as starting materials in producing the siloxanes of this invention contain a group that is represented by the formula:

T (7) wherein R, R', R" and n have the above-defined meanings and the nitrogen atom is interconnected to silicon through at least three carbon atoms. Illustrative of the groups represented by Formula 7 are the gamma-aminopropylsiloxy, para-aminophenylsiloxy, N-methyl delta aminobutylsiloxy, aminomethylphenyldiphenylsiloxy,

delta-aminobutyl(diphenyl)siloxy, epsilon aminopentyl- (methyl) siloxy, N-propyl-para-aminophenyl (ethyl) siloxy, N-ethyl-gamma-aminopropylsiloxy, delta aminobutylsiloxy and para-aminophenyl (methyl)siloxy groups and the like.

Suitable starting siloxanes include both those siloxaues that are composed solely of groups represented by Formula 7 and those siloxanes that contain one or more groups represented by Formula 7 together with one or more groups represented by Formula 3.

The polymers of this invention that are produced by hydrolyzing and condensing those hydrocarbonoxysilanes and siloxanes of this invention wherein the phosphorus atom is bonded to at least one hydrocarbonoxy group (i.e. those silanes and siloxanes of this invention wherein at least one Z in the Formula 1 or 2 is a hydrocarbonoxy group, contain a group that is represented by the formula:

wherein R, R and R" have the above-defined meanings and p is l or 2. In such groups the phosphorus atom provides a link in the polymeric chain and Y is XR tor OR.

Each silicon atom in the groups represented by Formula 8 can be linked through oxygen only to silicon or phosphorus or can be linked through oxygen to both silicon and phosphorus of another group or groups repre- 6 sented by Formula 8 to provide links in the polymeric chain. The phosphorus atom in Formula 8 can be linked through oxygen only to silicon or phosphorus or can be linked through oxygen to both silicon and phosphorus of another group or groups represented by Formula 8 to provide links in the polymeric chain. Such polymeric chains can be cyclic or can be terminated by hydroxyl or hydrocarbonoxy groups linked to a silicon atom or to the phosphorus atom. Such polymeric chains can also be terminated by an R SiO group linked to a silicon atom in the group represented by Formula 8.

When the phosphorus atom in the group represented by Formula 8 is linked through oxygen to silicon atom of other group represented by Formula 8, the groups so linked can be depicted (in the case where p is 2, and n is wherein R, R and R" have the above-defined meanings.

When the phosphorus atom in the :group represented by Formula 8 is linked through oxygen to the phosphorus atoms of other groups represented by Formula 8, the groups so linked can be depicted (in the case where p is 2 and n is 2) by the formula:

wherein R, R and R" have the above-defined meanings.

Illustrative of the polymers of this invention that contain a group represented by Formula 8 are polymers which can be produced by the hydrolysis and condensation of the silane,

CH CH3 (0 1140) P-fiI-CH CH CH di-O 0,115

(111. Such polymers contain the group CH3 CH3 OPI IOH CH CH S i0o.5

The hydrolysis and condensation reactions whereby polymers containing groups represented by Formula 8 are produced involve the reaction of a suitable hydrocarbonoxysilane or a suitable siloxane of this invention with water to hydrolyze the POR and, in the case of the silanes, the SOR groups in the former compounds to form POH groups and SiOH groups which condense to form the polymer. The amount of water employed in the hydrolysis and condensation is at least one mole for each mole of SiO-Si, Si-OP and P-O-P linkages desired to be produced (i.e., one mole of water for each two moles of silicon-bonded and/or phosphorusbonded hydrocarbonoxy groups desired to be hydrolyzed to form silicon-bonded hydroxyl groups which condense with each other to form the SiO-4i; Si-OP or PO-P linkages). A small excess of water over and above amount is preferred for speed and ease of reaction. Of course, silicon-bonded and phosphorus-bonded hydrocarbonoxy groups can be present in the polymer, if desired, by incompletely hydrolyzing the silicon-bonded and phosphorus-bonded hydrocarbonoxy groups by using lesser amounts of water. Silicon-bonded and phosphorusbondedhydroxyl groups can be present in the polymer if desired, by incompletely condensing the hydroxyl groups formed by hydrolysis. Such incomplete condensation is effected by using a large excess of water and short reaction times in the hydrolysis and condensation.

The hydrolysis and condensation reactions whereby are produced polymers containing groups represented by Formula 8 can be conducted at temperatures from C. to 250 C. Temperatures in the range of about 50 C. to 150 C. are preferred in order to hasten the hydrolysis and condensation without thermal decomposition. A solvent is preferably employed to provide ease of handling the reaction mixture. Suitable solvents are the liquid hydrocarbons, e.g., toluene, benzene, xylene and the like), alcohols e.g., ethanol, iso-propanol and the like) and ethers (e.g., di-isopropyl ether, diethyl ether and the like).

In producing polymers containing groups represented by Formula 8, it is desirable, particularly where the hydrocarbonoxy group or groups represented by Z are of relatively high molecular weight, to accelerate the rate of the hydrolysis and condensation reaction by employing a catalyst. By way of illustration, from about 0.5 to 3 percent by weight (based on the water reacted) of an inorganic acid (such as hydrochloric acid or sulfuric acid) can be used as a catalyst.

The polymers of this invention that contain groups that are represented by Formula 8 can be isolated by conventional means. Thus, after completion of the hydrolysis and condensation, low boiling materials such as water, alkanol by-products, solvents and the like can be removed from the reaction mixture by conventional means (e.g. distillation at reduced pressure) leaving the polymer as a residue. It should be understood that polymers containing groups represented by Formula 8 are mixtures of compounds and from which can be separated (e.g., by extraction or fractional crystallization) compounds containing only a particular type grouping (e.g. phosphorus combined only in PO-P or only in I PO-Si linkages).

, The polymers of this invention that contain groups represented by Formula 8 can also contain one or more groups represented by Formula 3. The latter groups are present in these polymers when silanes having the formula R Si(OR) (where R and x have above-defined meanings, are cohydrolyzed and cocondensed along with a suitable (i.e. POR containing) silanes or siloxanes of this invention in the production of the polymers. Alternately a group or groups represented by Formula 3 are present in the polymer if suitable starting siloxanes of this invention are employed that contain a group or groups represented by Formula 3.

When suitable starting siloxanes of this invention are employed in producing polymers containing groups represented by Formula 8 (i.e., those containing POR groups), little or no SiOR or SiOH groups may be initially present to react to form ESi-0-P linkages. However, ESi--O--SiE linkages in the siloxane can react with the water and alcohol (i.e. the alcohol formed by the hydrolysis of POR) to produce SiOR and/or Si--OH. The presence of POH groups catalyzes such reactions of the normally stable Si0'-Si linkage.

Phosphorus-bonded monovalent hydrocarbon and halogen-substituted monovalent hydrocarbon groups have greater hydrolytic stability than phosphorus-bonded hydrocarbonoxy groups. Consequently, when a silane of this invention wherein Z is only a monovalent hydrocarbon or a halogen-substituted monovalent hydrocarbon group, is hydrolyzed and condensed according to the above-described procedure, the product is the corresponding siloxane of this invention containing a phosphorusbonded monovalent hydrocarbon group or halogen-substituted monovalent hydrocarbon group.

The compounds of this invention are useful as lubricants and as additives to lubricants for improving the lubricity thereof. In particular, they can be added to organopolysiloxane lubricating fluids for imparting improved lubricity thereto. The siloxanes containing groups represented by Formula 2 and the polymers containing groups represented by Formula 8 are also useful as flame and solvent resistant protective coatings, particularly on metals such as steel, copper and aluminum. Such siloxanes and polymers can be formed in situ on the metal surface or can be preformed and then applied as adilute solution to the metal surface. After drying and curing the coating protects the metal even under severely corrosive, wet and dry conditions.

The following examples illustrate the present invention.

Example 1 One mole (221 grams) of gamma-aminopropyltri ethoxysilane and one mole (101 grams) of triethylamine were added to a kettle fitted with a stirrer, condenser and dropping funnel. One half mole (89.5 grams) of C H PCl was charged to the dropping funnel. The C H PCl was added slowly over a period of about 10 minutes to the kettle with stirring. The temperature increased from about 22 C. to 97 C. Triethylamine hydrochloride precipitated out immediately upon commencement of the addition. The reaction mixture was filtered while warm. The filtrate crystallized upon cooling to room temperature. An 82 per cent yield (222 grams) of the crystallized product was obtained. This product had the formula, C H P[NH(CH Si(OEt) and had a pH of about 8. Elemental analysis for carbon, hydrogen, silicon, phosphorus and nitrogen and infra-red analysis confirmed the composition and structure of the product.

' When one mole of delta-aminobutyl(diphenyl)ethoxysilane and one-half mole of C H PCl are reacted in the presence of one mole of triethylamine following the procedure described in Example 1, there is obtained a product having the formula The formula is confirmed by standard elemental and infra-red analysis and cryoscopic molecular weight determinations.

Example 3 Employing a similar procedure to that employed in Example 1, one mole of gamma-aminopropyltriethoxysilane and one mole of (C H PCl are reacted in the presence of one mole of triethylamine. silane of this invention having the formula,

( s s z 2) s 2 5) a The formula is confirmed by standard elemental and infra-red analysis and cryoscopic molecular weight diterminations.

Example 4 When one mole of epsilon-aminopentyl(methyl) dipropoxysilane and one-half mole of C H OPCl are reacted. in the presence of one mole of triethylamine in accordance with a procedure similar to that described in To produce a 9 Example 1, there is obtained a silane of this invention having the formula The formula is confirmed by standard elemental and infrared analysis and cyroscopic molecular weight determinations.

Example 5 When two moles of a siloxane having the formula:

CH3 CH3 HI I(CHz)aS iSi(CH H.

one mole of C H OPCl and two moles of trimethylamine are dissolved in toluene and the solution is heated for 0.5 hour at 100 C. there is produced a solution which can be filtered and stripped of toluene to produce a siloxane of this invention having the formula:

The formula is confirmed by standard elemental and infra-red analysis and cryoscopic molecular weight determinations.

Example 6 When 3.0 moles of a silane of this invention that is represented by the formula is dissolved in toluene and the solution so formed is mixed with 1.5 moles of water containing one percent by weight of hydrochloric acid and the mixture so formed is maintained at about 20 C. with stirring for about two hours, there is produced a polymer of this invention composed of groups having the formula:

The polymer so formed can be isolated by separating the toluene, ethanol and any unreacted water therefrom by heating at 40 C. and 50 mm. of Hg pressure. The formula of this compound can be confirmed by standard infra-red and elemental analysis and cryoscopic molecular weight determinations.

Example 7 When five parts by weight of either a siloxane of this invention (e.g. the siloxane produced as described in Example or a polymer of this invention (e.-g. the polymer produced as described in Example 6) is dissolved in 100 parts by weight of toluene and the solution so formed is sprayed on a steel surface according to conventional coating techniques, there is produced, upon volatilization ofthe toluene, a coating on the steel surface which protects the steel surface from corrosion.

Example 8 ing of the monovalent hydrocarbon groups, the halogensubstituted monovalent hydrocarbon groups and the hydrocarbonoxy groups; R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R" is a divalent hydrocarbon group, m is an integer from 0 to 2 inclusive, n' is an integer from 0 to 2 inclusive and each nitrogen atom is interconnected to silicon through at least three carbon atoms.

2. The hydrocarbonoxysilane of claim 1 wherein Z is a hydrocarbonoxy group containing from 1 to 18 carbon atoms and R is an alkylene group containing flom 3 to 5 carbon atoms.

3. The hydrocarbonoxysilane of claim 1 wherein R' is a hydrogen atom and R" is an alkylene group containing from 3 to 5 carbon atoms.

4. The hydrocarbonoxysilane of claim 1 wherein R" is an alkylene group containing from 3 to 5 carbon atoms, m is 2 and n is O.

5. The hydrocarbonoxysilane of claim 1 wherein R is an alkylene group containing from 3 to 5 carbon atoms, m is 2 and n is 1.

6. The hydrocarbonoxysilane of claim 1 wherein R" is an alkylene group containing from 3 to 5 carbon atoms, mis2andnis'2.

7. The hydrocarbonoxysilane represented by the formula:

C H P[NH( H2)aSi( 2 92]: 8. A siloxane comprising groups represented by the 2 iS-m wherein Z is a member selected from the group consisting of the monovalent hydrocarbon groups, the halogensubstituted monovalent hydrocarbon groups and the hydrocarbonoxy groups, R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R" is a divalent hydrocarbon group, m is an integer from 0 to 2 inclusive, n is an integer from 0 to 2 inclusive and each nitrogen atom is interconnected to silicon through at least three carbon atoms.

9. The siloxane of claim 8 wherein Z is a hydrocarbonoxy group and R" is an alkylene group containing from 3 to 5 carbon atoms.

10. The siloxane of claim 8 wherein R is a hydrogen atom and R" is an alkylene group containing from 3 to 5 carbon atoms.

11. The siloxane of claim 8 wherein R" is an alkylene group containing from 3 to 5 carbon atoms, m is 2 and n is 0.

12. The siloxane of claim 8 wherein R" is an alkylene group containing from 3 to 5 carbon atoms, in is 2 and n is 1.

13. The siloxane of claim 3 wherein R" is an alkylene group containing from 3 to 5 carbon atoms and n is 2.

14. A siloxane comprising groups represented by the formula:

wherein Z is a member selected from the group consisting of the monovalent hydrocarbon groups, the halogenvsubstituted monovalent hydrocarbon groups and the hydrocarbonoxy groups, R is a monovalent hydrocarbon group, R is a member selected from the groupconsisting of the hydrogen atom and the monovalent hydrocarbon groups, R" is a divalent hydrocarbon group, m is an integer from 0 to 2 inclusive, n is an integer from 0 to 2 inclusive and each nitrogen atom is interconnected to 1 1 silicon through at least three carbon atoms and (b) groups represented by the formula:

Rxslo4 x wherein R has the above-defined meaning and x has a value from O to 3 inclusive.

15. The siloxane of claim 14 wherein R is a methyl group.

16. A polymer comprising polymeric units represented by the formula:

wherein Y is a member selected from the group consisting of the monovalent hydrocarbon groups and the halogen-substituted monovalent hydrocarbon groups; R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups; R", is a divalent hydrocarbon group; n is an integer from to 2 inclusively; p is an integer from 0 to 1; each nitrogen atom is interconnected to silicon through at least three carbon atoms; and the phosphorus atom and each silicon atom is bonded through oxygen to a member selected from the group consisting of phosphorus and silicon of another group represented by said formula.

17. The polymer of claim 16 wherein R is a hydrogen atom, R" is an alkylene group containing from 3 to 5 carbon atoms, 12 is 2 and n is 0.

18. The polymer of claim 16 wherein R is a hydrogen atom, R" is an alkylene group containing from 3 to 5 carbon atoms, p is 2 and n is 1.

19. The polymer of claim 16 wherein R is a hydrogen atom, R is an alkylene group containing from 3 to 5 carbon atoms, p is 2 and n is 2.

20. A process for producing the polymer of claim 16,

which comprises hydrolyzing and condensing a hydrocarbonoxysilane represented by the formula:

R R5 i R- sOR,.-.]..

wherein Z is a member selected from the group consisting of the monovalent hydrocarbon groups, the halogensubstituted monovalent hydrocarbon groups and the hydrocarbonoxy groups; R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R is a divalent hydrocarbon group, m is an integer from 0 to 2 inclusive, n is an integer from 0 to 2 inclusive and each nitrogen atom is interconnected to silicon through at least three carbon atoms.

21. A process for producing the polymer of claim 16, which comprises hydrolyzing and condensing a siloxane comprising groups represented by the formula:

wherein Z is a member selected from the group consisting of the monovalent hydrocarbon groups, the halogensubstituted monovalent hydrocarbon groups and the hydrocarbonoxy groups, R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R is a divalent hydrocarbon group, m is an integer from 0 to 2 inclusive, n is an integer from 0 to 2 inclusive and each nitrogen atom is interconnected to silicon through at least three carbon atoms.

22. A process for producing a hydrocarbonoxysilane represented by the formula:

wherein Z is a member selected from the group consisting of the monovalent hydrocarbon groups, the halogensubstituted monovalent hydrocarbon groups and the hydrocarbonoxy, groups, R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R is a divalent hydrocarbon group, m is an integer from 0 to 2 inclusive, n is an integer from 0 to 2 inclusive and each nitrogen atom is interconnected to silicon through at least three carbon atoms, which process comprises reacting (I) a phosphorus compound having the formula:

wherein X is a halogen atom and Z and m have the above-defined meanings and (II) a silane having the formula:

wherein R, R', R" and n have the above-defined meanings. 23. A process for producing a siloxane comprising groups represented by the formula:

wherein Z is a member selected from the group consisting of the monovalent hydrocarbon groups, the halogensubstituted monovalent hydrocarbon groups and hydrocarbonoxy groups, R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R" is a divalent hydrocarbon group, In is an integer from 0 to 2 inclusive,,n is an integer from 0 to 2 inclusive and each nitrogen atom is interconnected to silicon through at least three carbon atoms, which process comprises reacting (I) a phosphorus compound having the formula:

wherein X is a halogen atom and Z and m have the above-defined meanings and (II) a siloxane comprising groups having the formula:

t e HNR"SiO wherein R, R, R" and n have the above-defined meanings.

References Cited by the Examiner UNITED STATES PATENTS 2,920,094 1/ 60 Fekete 260--448.2 2,934,550 4/60 Jack 260448.2 2,951,860 v 9/60 Plueddemann 260-4482 2,963,503 12/60 Marsden 260-465 2,978,471 4/ 61 Fekete 26046.5

MURRAY TILLMAN, Primary Examiner.

MILTON STERMAN, WILLIAM H. SHORT,

Examiners. 

8. A SILOXANE COMPRISING GROUPS REPRESENTED BY THE FORMULA: 